US7851653B2 - Method of creating a solvent-free polymeric silicon-containing quaternary ammonium antimicrobial agent having superior sustained antimicrobial properties - Google Patents
Method of creating a solvent-free polymeric silicon-containing quaternary ammonium antimicrobial agent having superior sustained antimicrobial properties Download PDFInfo
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- US7851653B2 US7851653B2 US11/386,485 US38648506A US7851653B2 US 7851653 B2 US7851653 B2 US 7851653B2 US 38648506 A US38648506 A US 38648506A US 7851653 B2 US7851653 B2 US 7851653B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24909—Free metal or mineral containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
- Y10T428/257—Iron oxide or aluminum oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
Definitions
- This invention relates to a novel silicon-containing antimicrobial polymer composition and to a method of creating a solvent-free formulation of such polymeric antimicrobial material, preferably in the form of a dry powder or in solution in a solvent in order to impart antimicrobial activity unto or in another material.
- the antimicrobial polymer has superior antimicrobial properties compared to the similar monomer.
- this invention relates to a novel way to form an antimicrobial material that can be incorporated in or bound to a substrate such that it has a non-leaching antimicrobial property that is not dependent on the mechanism of leaching antimicrobial agents.
- the method described herein may be used to prepare or treat biocompatible devices or other products and impart antimicrobial properties to substrates containing the antimicrobial agent throughout the polymeric substrates. Additionally, the method described herein may be used to prepare or treat biocompatible devices or other products and impart antimicrobial properties to polymeric substrates containing the antimicrobial agent bound to the surface of the polymeric substrates. Further, the method described herein may be used to prepare liquid solutions with antimicrobial properties.
- Silicon-containing quaternary ammonium antimicrobial agents belong to a general class of antimicrobial agents termed cationic antimicrobial agents.
- This invention relates to a solvent-free polymer composition and to a method of creating a polymeric silicon-containing quaternary ammonium antimicrobial agent that is more effective than the monomeric form in solutions.
- an “antimicrobial agent” is an agent that destroys or inhibits the growth of microorganisms, and particularly pathogenic microorganisms.
- the major classes of microorganisms are bacteria, fungi including mold and mildew, yeasts, and algae. Microorganisms can be found in the air, the water, in and on the human body and bodies of animals, soil, wastes, and on all surfaces.
- microorganisms are deposited from the air, food and drink spills, dust, and dirt and tracked in soil, and from human and animal excreta such as sweat, urine, and feces.
- Organisms grow and multiply when there is available a nutrient source of food such as organic or inorganic material contained in such wastes, dirt, dust, and living tissue.
- a nutrient source of food such as organic or inorganic material contained in such wastes, dirt, dust, and living tissue.
- most microorganisms also require warm temperatures, and moisture. When these conditions exist, microorganisms multiply, grow and flourish. Microbial growth, however, leads to many problems, such as unpleasant odors ranging from stale to musty and mildew-like, to putrid and foul smelling, resembling ammonia.
- the growths also produce unsightly stains, discoloration, and deterioration of many surfaces and materials in which they come into contact.
- a more serious disadvantage of microbial growth is the proliferation of pathogenic microorganisms, their metabolic products and their somatic and reproductive cell parts, which contribute to the spread of disease, infection, and health disorders.
- Silicon-containing quaternary ammonium salts having the following Formula I are recognized antimicrobial agents: R 3 N + R 0 n SiX 4-n Y ⁇ (I) Wherein each R and each R 0 is independently, a non-hydrolysable organic group; each X is, independently, a hydrolysable group; n is an integer of 0 to 3; and Y is a suitable anionic moiety to form the salt of the compound of Formula I.
- Such silicon containing quaternary ammonium antimicrobial agents are typically manufactured and supplied in solvents such as methanol.
- silicon-containing quaternary ammonium antimicrobial compounds are available and widely used as disinfectants and biocides and to treat items that may undesirably support microbial growth.
- methanol-containing, silicon-containing quaternary ammonium salts are used to treat carpeting, walls, various commercial products such as sponges and fabrics, and even water. They are also used to rehabilitate “sick buildings,” particularly after floods and water leaks, and reduce odors caused by mildew, fungi and bacterial growth in damp basement areas.
- silicon-containing quaternary ammonium salts are generally pre-packaged in water or alcohol solutions of approximately 2 weight % to approximately 3 weight %, or less, quaternary salt concentration. They are applied to substrates, such as carpets, walls and floors, to kill the bacteria.
- the silicon-containing quaternary ammonium salt is often applied in a fine spray.
- concentration of the quaternary ammonium salt generally can be much lower, e.g., less than 1 weight %.
- antimicrobial surface treatments use a coating treatment that provides a vehicle for entrapping the antimicrobial agent on the surface but permits subsequent diffusion of the antimicrobial agent into the biological environment. Many such treatments rely upon a leaching mechanism to deliver the antimicrobial agent into the environment.
- a method has not been devised to impart to a substrate a non-leaching, biocompatible, chemically bonded antimicrobial properties throughout the entire substrate. Only the very surface has previously been made antimicrobial with a non-leaching antimicrobial agent through the formation of an interpenetrating network at the interface of the substrate surface and the antimicrobial agent, for only as deep into the surface as the antimicrobial agent could be adsorbed into the substrate.
- the present invention of chemically bonding or physically mixing a silicon-containing quaternary ammonium salt of Formula II (below) and a polymeric substrate, preferably in the form of a bulk resin substrate so made and methods of using such bulk resin accomplishes this goal.
- antimicrobial properties imparted to a material resulting from the present invention and its use are “sustained” when such material has long-lasting, non-leaching, antimicrobial properties not only on the surface, but also throughout the material, substrate, formed plastic product, device or other product made containing the antimicrobial agent of the present invention, if and when it is worked, molded, machined, abraded or otherwise formed into any desired product.
- whatever portion of the product made according to the present invention becomes the surface of such product after working, molding, machining, abrading or other forming or manufacturing process, the surface with which humans and animals have contact will be an antimicrobial surface.
- Such materials containing the antimicrobial polymer made using the present invention are not toxic to humans or animals.
- antimicrobial polymers of polymerized silicon-containing quaternary ammonium salt monomers have not been incorporated into medical polymers, thin layer films or laminates in hospitals or on medical devices and supplies to impart antimicrobial properties to such devices and supplies.
- the present invention accomplishes this in such a manner that does not compromise their biocompatibility.
- the present invention relates to a method for creating a solvent-free polymeric antimicrobial agent for manufacture of medical devices and supplies that is biocompatible and antimicrobial throughout the entire composition of the device or supply.
- the present invention also relates to a method for creating a solvent-free polymeric antimicrobial agent for manufacture of medical devices and supplies that is biocompatible and antimicrobial on the surface of the device or supply.
- the present invention also relates to a method for creating a solvent-free polymeric antimicrobial agent for manufacture of fabrics for clothing, outerwear, underwear, carpets, draperies, furniture and other articles containing fabric.
- the present invention also relates to a method for creating an antimicrobial agent for liquid solutions.
- the present invention additionally relates to a method for creating an antimicrobial agent for manufacture of a filter medium such as activated carbon, fiberglass, sand, fabrics and HEPA filtering materials.
- a filter medium such as activated carbon, fiberglass, sand, fabrics and HEPA filtering materials.
- the present invention also relates to a method for creating a biocompatible and solvent-free polymeric antimicrobial material for building materials, including paint thin films; and consumer products.
- the present invention further relates to an antimicrobial laminate counter top that is not dependent on leaching antimicrobial agents for surface microbial protection.
- the polymer of Formula II may be linear, cyclic, branched or cross-linked into three-dimensional networks.
- the present invention additionally provides a method for creating a polymeric thin layer film or laminate having antimicrobial properties that can be applied to various medical and food supply surfaces.
- One aspect of the present invention relates to an antimicrobial polymer containing silicon-containing quaternary ammonium groups, the polymer comprising in its structure repeating units of Formula II: R 3 N + R 0 n SiX′ 4-n Y ⁇ (II) wherein each R and each R 0 is independently a non-hydrolysable organic group; each X′ is —OR′, —OH or —O—Si, wherein R′ is an alkyl group of 1 to about 22 carbon atoms, or an aryl group of 6 carbon atoms; n is an integer of 0 to 3; and Y is an anionic moiety suitable to form the salt of the repeating units of Formula II.
- embodiments of the present invention include a method to produce a novel composition of a solvent-free polymeric form of silicon-containing quaternary ammonium antimicrobial agents.
- the resulting solid polymers provide enormous benefit in allowing the antimicrobial to be blended with as example; bulk resins, coatings, and laminates during their processing.
- the antimicrobial agent is incorporated throughout the treated material giving a non-leaching permanence, namely, sustained antimicrobial properties.
- the prior art teaches avoiding polymer formation from the monomeric silicon-containing quaternary ammonium salts because the polymer was no longer in a viable form to treat articles.
- Past experience with the monomer showed that upon exposure to water the molecular weight increase due to polymer formation resulted in an intractable form that could not be used.
- This invention eliminates these problems and provides an antimicrobial with many advantages in terms of incorporation into treated products, increased antimicrobial performance and reducing cost.
- Binder resin means a resin in any form, such as pellets, beads, flakes or powder or the like, prior to forming into a product. Often additives are blended with the bulk resin prior to forming to impart such properties as: antimicrobial, antioxidation, UV resistance, color, fire retardance, etc.
- Form plastic product means a polymeric resin that has been formed into a shape using various molding, extrusion, pultrusion or other forming techniques.
- Polymer means a large molecule built up by the repetition of small chemical units (monomers). The resulting chains can be linear, cyclic, branched or cross-linked into three-dimensional networks.
- Resin means a synthetic polymeric plastic that may be thermoplastic or thermosetting.
- “Substrate” means a product to which the antimicrobial silicon-containing quaternary ammonium salt is applied or with which it is mixed or otherwise blended or reacted to impart the substrate with sustained antimicrobial properties.
- Thermoplastic polymer or resin means a polymer where no chemical bonds form with other chains. The polymer will melt with the addition of heat.
- Thermoset polymer or resin means a polymer where chemical bonds form between chains resulting in a 3-dimensional cross-linked structure. These polymers do not melt.
- one aspect of the present invention relates to an antimicrobial polymer containing silicon-containing quaternary ammonium groups, the polymer comprising in its structure repeating units of Formula II: R 3 N + R 0 n SiX′ 4-n Y ⁇ (II) wherein each R and each R 0 is independently a non-hydrolysable organic group; each X′ is —OR′, —OH or —O—Si, wherein R′ is an alkyl group of 1 to about 22 carbon atoms, or an aryl group of 6 carbon atoms; n is an integer of 0 to 3; and Y is an anionic moiety suitable to form the salt of the repeating units of Formula II.
- One method of the present invention uses the technology of polymerizing a silicon-containing quaternary ammonium salt monomer to create a polymer with two or more silicon-containing quaternary ammonium salt repeating units to form a homopolymer in solution or as a solid.
- the resulting polymer has superior antimicrobial properties compared to the source monomer.
- the preferred silicon-containing quaternary ammonium salt monomer used to make the polymer of Formula II has a Formula I: R 3 N + R 0 n SiX 4-n Y ⁇ (I) wherein each R and each R 0 is independently, a non-hydrolysable organic group; each X is, independently, a hydrolysable group; n is an integer of 0 to 3; and Y is a suitable anionic moiety to form the salt of the compound Formula I.
- Y is a halide.
- the presently most preferred silicon-containing quaternary ammonium salt is where two of the Rs are methyl and one R is octadecyl, R 0 is propyl, each X is a methoxy, n is 1 and Y is chloride, such that the monomeric quaternary ammonium salt is 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride.
- the quaternary ammonium salt monomer is selected from the group consisting of one of Formula III or IV: (R 1 ) 3 SiR 2 N + (R 3 )(R 4 )(R 5 )Y ⁇ (III); (R 1 ) 3 SiR 2 N(R 3 )(R 4 ) (IV); wherein each R 1 is, independently, halogen or R 6 O, where R 6 is H, alkyl of 1 to about 22 carbon atoms, acetyl, acetoxy, acyl, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; a block polymer or copolymer of ethylene and propylene glycol, an alkyl monoether of 1 to about 22 carbon atoms of propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; a block polymer or copolymer of ethylene and propylene glycol or the monoester of a carbonic acid of 1 to about 22 carbon
- R 2 is benzyl, vinyl or alkyl of 1 to about 22 carbon atoms
- R 3 and R 4 are, independently, lower alkyl alcohol of 1 to about 6 carbon atoms, lower alkoxy of 1 to about 6 carbon atoms, alkyl of 1 to about 22 carbon atoms; or R 3 and R 4 can, together, form a morpholine or cyclic or heterocyclic, unsaturated or saturated, five to seven-member ring of the Formula V: —R 3 —(R 7 ) k —R 4 — (V)
- k is an integer from 0 to 2
- R 7 wherein R 7 , where the ring is saturated, is CH 2 , O, S, NH, NH 2 + , NCH 2 CH 2 NH 2 , NCH 2 CH 2 NH 3 + , NCH 2 CH 2 N(R 8 )(R 9 ), NCH 2 CH 2 N + (R 8 )(R 9 )(R 10 ), N(alkyl), N(aryl), N(benzyl), wherein each R 8 , R 9 , and R 10 is, independently, benzyl, polyether, lower alkyl alcohol of 1 to 4 carbon atoms, lower alkoxy of 1 to 4 carbon atoms, or alkyl of 1 to about 22 carbon atoms, and wherein R 7 , where the ring is unsaturated, is CH, N, N + H, N + (alkyl), N + (aryl), N + (benzyl), NCH 2 N, N + HCH 2 N, N + (alkyl)CH 2 N, N + (aryl)CH 2 N,
- ring is unsubstituted or substituted with alkyl of 1 to 22 carbon atoms, ester, aldehyde, carboxylate, amide, thionamide, nitro, amine, or halide;
- R 5 is lower alkyl alcohol of 1 to 6 carbon atoms, CH 2 C 6 H 5 , polyether, alkyl, alkoxy, perfluoroalkyl, pefluoroalkylsulfonate or perfluoroalkylcarboxylate, wherein the alkyl, alkoxy, perfluoroalkyl, perfluoroalkylsulfonate or perfluoroalkylcarboxylate is of 1 to about 22 carbon atoms, or is a five to seven-member ring of Formula V as described above; and
- Y ⁇ is a suitable anionic moiety to form the salt of the compound of Formula III or IV, and preferably, chloride, bromide or iodide.
- the resultant silicon-containing quaternary ammonium salt polymer has repeating units of Formula II: R 3 N + R 0 n SiX′ 4-n Y ⁇ (II)
- the presently most preferred silicon-containing quaternary ammonium salt repeating unit is where two of the Rs are methyl and one R is octadecyl, R 0 is propyl, n is 1 and Y is chloride, such that the polymer is polymeric 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride.
- One method of preparing the preferred silicon containing quaternary ammonium polymer includes adding with agitation the silicon containing monomer to an excess of solvent, such as water, along with heat and/or a catalyst such as a mineral or organic acid or base, which initiates the polymerization process.
- solvent such as water
- a catalyst such as a mineral or organic acid or base
- one embodiment of the method of making the polymer having repeating units of Formula II comprises:
- an embodiment of the method further comprises a preliminary step before step (a) that comprises dissolving the monomeric silicon-containing quaternary ammonium salt in a solvent to form a solution;
- the hydrolysis steps (b) further comprises mixing the solution and water preferably in the presence of heat and/or a catalyst;
- the condensation step (c) preferably further comprises subjecting the solution undergoing hydrolysis to heat and/or removal of water or the other solvent to drive the reaction further to completion to form the polymer;
- the method further comprises a step (d) of recovering the polymer by one of precipitation and solvent removal.
- a preferred further step is step (e) of drying the recovered polymer, preferably by heating to evaporate the solvent, resulting in the polymer being solvent-free, where solvent-free means that the polymer may contain residual solvent up to about 10 weight percent of the polymer.
- the solvent is any suitable solvent, such as, without limitation, water, an alcohol, such as ethanol, propanol, isopropanol or butanol, a ketone, such as methyl ethyl ketone, an aldehyde, such as butyl aldehyde, an aliphatic hydrocarbon, such as pentane or hexane, an aromatic hydrocarbon, such as toluene or xylene, a glycol ether, such as diethylene glycol monomethyl ether or ethylene glycol dibutyl ether, and a halogenated hydrocarbon, such as 1,1,1-trichloroethane or tetrachloroethane.
- a suitable solvent such as, without limitation, water, an alcohol, such as ethanol, propanol, isopropanol or butanol, a ketone, such as methyl ethyl ketone, an aldehyde, such as butyl aldehy
- Exemplary preferred solvents include, without limitation, water, alcohols such as isopropyl alcohol and t-butyl alcohol, tetrahydrofuran, chloroform, carbon tetrachloride, ethylene glycol, propylene glycol and ethyl acetate. If water is the only solvent, there is a molar excess to hydrolyse the Si—OR groups to Si—OH. If the reaction is conducted in another solvent, a stoichiometric amount of water is then added to hydrolyse the Si—OR groups.
- the catalyst is a mineral acid, an organic acid or a base.
- the acid is hydrochloric acid, sulfuric acid or acetic acid.
- the base is sodium hydroxide, potassium hydroxide, ammonium hydroxide, an aliphatic amine, such as dimethylamine, tetramethylenediamine or hexamethylenediamine, a cycloaliphatic amine such as morpholine or cyclohexylamine, or an aryl amine such as aniline or diphenylamine.
- polymer is a copolymer of one of a monomer and a host polymer and a polymer having repeating units of Formula II: R 3 N + R 0 n SiX′ 4-n Y ⁇ (II) wherein X′ is OH; and wherein the monomer and host polymer comprise functional groups capable of reacting with SiOH groups to form the copolymer.
- Suitable functional groups of the monomer and host polymer may include, without limitation, —OH, —C(O)OH, —NH 2 , —NH, —NCO or —C(O)OR 11 , wherein R 11 may be an aliphatic, a cycloaliphatic or an aryl group.
- R 11 may be an aliphatic, a cycloaliphatic or an aryl group.
- examples of such groups include an aliphatic group, such as an alkyl group of 1 to about 22 carbon atoms, for instance methyl, ethyl, propyl, butyl, octyl or dodecyl; a cycloaliphatic group, such as cyclopentane or cyclohexane; or an aryl group, such as phenyl.
- the antimicrobial silicon-containing quaternary ammonium salt solution includes as a solvent for the antimicrobial agent any solvent that may effectuate the conversion of the hydrolysable groups, such as the methoxy groups, on the silicon-containing quaternary ammonium salt to OH groups.
- the solvent is selected based on its ability to dissolve the antimicrobial silicon-containing quaternary ammonium salt.
- the concentration of the solution may be about 1% to about 99% by weight of the antimicrobial silicon-containing quaternary ammonium salt.
- about 1% to about 75% by weight of the antimicrobial silicon-containing quaternary ammonium salt is used, and more preferably about 1% to about 50% by weight is used.
- the silicon-containing quaternary ammonium salt is polymerized to form the antimicrobial homopolymer.
- Such polymerization preferably is achieved by mixing the solution of the silicon-containing quaternary ammonium salt monomer used to form the polymeric antimicrobial agent with a catalyst, which may be a base, such as those mentioned above, an acid, such as those mentioned above, or heat, or a combination of a base or acid and heat.
- the base and acid may have concentrations of about 0.0N to about 1N.
- An effective temperature for polymerization is about 10° C. to about 300° C., preferably about 30° C. to about 100° C., and more preferably about 20° C. to about 50° C. In general, the greater the temperature, the less time it takes for the antimicrobial polymer to form.
- the method of making the antimicrobial polymer described above creates a polymeric antimicrobial silicon-containing quaternary ammonium salt, which can be incorporated into resins and materials to create substrates with sustained antimicrobial properties.
- the solid antimicrobial polymer can be used to treat materials by different methods of incorporating the antimicrobial polymer into the materials. Such procedures may include, for example, without limitation:
- Types of applications for the antimicrobial polymer include as examples, but not limited to, a paint thin film for use with latex or other paints for painting any surface; a laminate; a medical product; a building material, such as a counter top, roofing products like shingles, floor or ceiling tile or wall covering, doorknob, toilet handle; packaging material; paper products, toys, furniture or any other product where antimicrobial properties are desired.
- Other products include various types of materials or substrates, such as thermoset polymeric resin, composition wood which may include synthetic polymeric components, such as oriented strand board; plywood; paper products, textiles, activated carbon, etc.
- types of resins that can be treated with the antimicrobial polymer are: polyvinyl chloride, polyurethane, urea formaldehyde, melamine formaldehyde, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic, polystyrene acrylic, polyvinyl acrylic, or any other suitable resin.
- the resin may be a thermoplastic resin or a thermoset resin.
- the solid form of the antimicrobial agent may be melt blended or the like with separate resin beads, etc., to form the desired antimicrobial bulk polymeric resin.
- blending which may be mixing, extrusion, pultrusion or the like, involves the use of a well known industrial mixer or extruder, such as but not limited to a Welex® mixer or Welex® extruder, available from Welex Incorporated, Blue Bell, Pa.
- the solid antimicrobial agent and the resin particles are added to the mixer in the desired proportions as set forth below and mixed at an elevated temperature where the components melt but do not degrade.
- the temperature should be sufficient to allow the formerly solid components to flow and uniformly blend with each other.
- the time to accomplish uniform blending such that a uniform mixture results varies based on the temperature and equipment used, but in general, should be sufficient to provide a uniform blend of the polymeric antimicrobial agent and the polymeric resin, whereby the resulting product will have sustained antimicrobial properties.
- a suitable temperature is preferably about 60° C. to about 350° C., more preferably about 100° C. to about 325° C., and even more preferably, about 150° C. to about 300° C.
- the mixing process results in the polymeric resin beads being evenly coated with or distributed uniformly and blended with the polymeric antimicrobial agent to form the antimicrobial bulk polymeric resin.
- the resulting polymeric resin has sustained antimicrobial properties that will continue to be sustained when the polymeric resin is formed into a substrate of any desired configuration, such as thin sheets for example, or any formed plastic product made from the substrate or directly from the polymeric resin.
- the polymerized silicon-containing quaternary ammonium salt is “anchored” to the resin and substrate through physical blending, van der Waals forces, and chemical covalent bonding, depending on the nature of the polymeric resin substrate.
- the presence of the active polymeric silicon-containing quaternary ammonium group with the polymeric resin substrate has been substantiated by a dye test using Bromophenol blue.
- the longevity or permanence of the quaternary ammonium group has been demonstrated by dye testing the treated material after repeatedly challenging the treated host substrate with multiple hot (e.g., 140° F., 60° C.) water rinses, aging treated samples with forced air or in a microwave oven, and subjecting the treated sample to repeated boiling water for 30 minutes.
- the concentration of the silicon-containing quaternary ammonium salt polymer should be less than about 50% by weight of the final bulk polymeric resin matrix to minimize adversely affecting properties of the host polymeric resin.
- the amount of antimicrobial agent to the host resin preferably is about 0.025% to about 50%, more preferably about 0.05% to about 20%, and even more preferably, about 0.15% to about 0.5%, where the percentages are weight percentages.
- the resin substrate may be formed from a resin concentrate where a resin with a high concentration of the antimicrobial silicon-containing quaternary ammonium salt polymer is blended with the resin without any of the antimicrobial silicon-containing quaternary ammonium salt polymer in concentrations such that the final blend contains the desired amount of antimicrobial silicon-containing quaternary ammonium salt polymer.
- a resin concentrate where a resin with a high concentration of the antimicrobial silicon-containing quaternary ammonium salt polymer is blended with the resin without any of the antimicrobial silicon-containing quaternary ammonium salt polymer in concentrations such that the final blend contains the desired amount of antimicrobial silicon-containing quaternary ammonium salt polymer.
- Such an antimicrobial bulk resin made from the solid polymer of the antimicrobial silicon-containing quaternary ammonium salt can be formed into a substrate of any desired shape or size using well-known plastic molding and extrusion techniques.
- Tubing is manufactured by adding the antimicrobial resin beads in an extrusion mixer, such as a Welex® extruder at an elevated temperature not to exceed 350° C. Molded parts can be made by adding the antimicrobial resin beads in an injection molder at temperatures not to exceed 350° C.
- a block of the antimicrobial polymer is prepared and properly machined to the desired device dimensions.
- the thin layer may have any desired dimensions, based on the available equipment used to make the product.
- the thin layer has a thickness of about 0.001 inch (0.025 mm) to about 3 inches (76.2 mm), preferably about 0.01 inch (0.25 mm) to about 1 inch (25.4 mm), and more preferably about 0.063 inch (1.6 mm) to about 0.25 inch (6.35 mm).
- Several layers could be made at the same time and pressed together to form a thicker layer or a laminated substrate. Multiple layers of the same material or different material can be formed into a laminate.
- the present invention includes the additive or preferably synergistic combination of antimicrobial agents comprising more than one polymeric silicon-containing quaternary ammonium salt with at least one other antimicrobial agent.
- antimicrobial agents may include, by way of example and not limitation, boric acid, polyhexamethylenebiguanide, hydantoin, a silver salt and a combination thereof.
- the independent laboratory determined the relative mole percentages of the corresponding T structures for the product of the present invention by integrating the areas under the respective peaks corresponding to the various T structures as set forth in the following Table A, indicating a predominant mole percentage of the T 3 structure:
- fumed silica (silica gel) were dispersed in 100 g of distilled water. 2.0 g of homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride prepared in Example 2 was added drop-wise at room temperature for ten minutes with vigorous stirring. The resulting modified silica was dried in a vacuum oven to produce methanol-free fumed silica polymerized with the silicon-containing quaternary ammonium salt.
- Antimicrobial testing of the cast PVC films of Example 4 was carried out essentially as described in the ASTM designation E 2149-01 entitled, “Standard test Method for Determining the Antimicrobial Activity of Immobilized Antimicrobial Agents under Dynamic Contact Conditions.” This test is designed to evaluate the antimicrobial properties of materials, which contain active agents that are non-leaching. The method is described briefly below.
- E. coli was grown overnight in rich media in an incubator-shaker at 37° C. while shaking at 300 rpm. After 18 hours of incubation, the bacteria were removed from the incubator and the optical density at 660 nm was measured. The culture was diluted until the optical density corresponds to a bacterial concentration of between 1 ⁇ 10 8 and 3 ⁇ 10 8 Colony Forming Units (CFU) per milliliter. The bacteria were further diluted in phosphate buffer (0.3 mM KPO 4 at pH 7.2) such that the working concentration was 1 ⁇ 10 6 to 3 ⁇ 10 6 CFU/mL. Test specimens were added to sterile 15 mL test tubes followed by the addition of 3 mL of the bacterial solution.
- CFU Colony Forming Units
- Log kill is a standard method to establish the ability of antimicrobial agents to destroy microorganisms.
- a log kill of 5.0 means that 100,000 microorganisms were destroyed on contact with the treated surface.
- a log kill of 6.0 establishes that 1,000,000 microorganisms were destroyed on contact with the treated surface.
- a log kill in excess of 5.0 is typically interpreted as an exceptionally active antimicrobial agent.
- the 0.2% cast film of Example 4 was found to have a log kill of 6.17 and the 0.5% cast film had a log kill of >6.30.
- polyurethane resin (Tecoflex 80A, Noveon Corp.) was dissolved in 100 g of tetrahydrofuran in a beaker. 0.20 g of dry homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride prepared in Example 2, was added and dissolved by stirring. The solution was cast on glass slides and dried in a vacuum oven at 95° C. The cast film was a methanol-free film of PU and the silicon-containing quaternary ammonium homopolymer. Antimicrobial testing was carried out as described in Example 5. The antimicrobial cast film was found to have a log kill of >6.98.
- polyacrylate resin beads 50 pounds (27.7 Kg) of polyacrylate resin beads were added to an open top tank. 45.4 g of homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride prepared is Example 2 was dissolved in isopropanol and subsequently added to the open top tank. The slurry was stirred for 5 minutes, producing polyacrylate resin beads evenly coated with the homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride. Homogeneity of the coating on the resin beads was demonstrated by the following bromophenol blue test.
- a 4% solution of PVOH (Celvol 103, Ciba-Geigy Corporation) in water was prepared by adding 4 g of PVOH to 100 g of distilled water. The solution was heated to 190° F. (87.8° C.) with continuous stirring to dissolve the PVOH. The solution was cooled to room temperature and 1.2 grams of the homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride in methanol prepared as in Example 2 were added drop-wise for ten minutes with vigorous stirring. The solution was heated to 80° F. (26.7° C.) and allowed to react for an additional ten minutes while stirring.
- the resulting polymer was concentrated to 5% (wt/wt) in a rotary evaporator. The solution was dried to a methanol-free dry powder. The antimicrobial activity of the resultant polymer was determined using the test method described in Example 5 and found to have a log kill of 5.54.
- polyacetal resin beads 50 pounds (27.7 Kg) of polyacetal resin beads were added to an open top tank. 11.4 g of homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride prepare as in Example 2 was dissolved in isopropanol and subsequently added to the open top tank. The slurry was stirred for 5 minutes, producing polyacetal resin beads evenly coated with the homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride. Homogeneity of the coating was established using the bromophenol blue test. The antimicrobial resin was extruded with a commercial extrusion machine to produce extruded bar stock. The bar stock was tested for antimicrobial activity according to the test described in Example 5 and found to exhibit a log kill of 6.22 against E. coli.
- Coconut shell activated carbon was treated with monomeric 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and polymeric 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as made in Example 2 to compare the relative effectiveness of the two treatment schemes.
- a ladder series of treated activated carbon using the monomer and the polymeric forms of the antimicrobial agent was prepared in a pilot reactor. They were treated at levels from 0.05% to 0.5% of the antimicrobial agent to activated carbon on a weight/weight basis.
- the treatment scheme involved dissolving the polymer and monomer in water at their respective levels.
- the dilute solutions of antimicrobial agents were sprayed on the 500 g of carbon surface using a fine mist.
- the monomer was further treated with catalytic quantities of dilute ammonium hydroxide to polymerize the monomer on the surface of the activated carbon. After the spraying process, drying the treated carbon at 300° F. (149° C.) for two hours activated the carbon.
- the antimicrobial activity of the carbon was determined using the standard dynamic shake flask test described in Example 5. Results are given in the following Table 1.
- CTC activity testing was performed by a vendor in accordance with ASTM Method D3467. The results of testing on six different samples in Table 1 indicated that there was only a marginal decrease in CTC activity after impregnation.
- the treated carbon was found to be very active at killing E. coli .
- the polymeric form of the antimicrobial agent is more active than the monomeric form.
- activated carbon as little as 0.05% by weight of the polymer is effective.
- Multipurpose printer paper was pad coated with a 0.05% water solution of homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride made according to Example 2. The paper was allowed to air dry. Subsequent antimicrobial testing as described in Example 5 confirmed that the paper exhibits antimicrobial properties with a log kill in excess of 4.0.
- Unbleached cotton fabric was treated with various concentration levels of both monomeric 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and the homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as prepared in Example 2.
- Table 2 gives the levels of treatment and the results of antimicrobial testing. In all cases 2 inch (5.1 cm) by 2 inch (5.1 cm) swatches of fabric were treated by immersing them in an aqueous solution containing the respective concentration of monomeric or polymeric 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride for a minimum of ten minutes.
- the swatches were subsequently removed from the aqueous solution and air-dried overnight.
- the swatches were analyzed for antimicrobial activity using ASTM E2149-01 as described in Example 5 followed by an accelerated laundering test according to AATCC 61-1996, which simulates multiple laundering effects.
- the swatches were again analyzed for antimicrobial activity according to ASTM E2149-01 to determine the effect of laundering on the antimicrobial activity. Results before and after laundering are given in the following Table 2. Antimicrobial activity is reported as percent reduction in E. coli concentration.
- An antimicrobial laminate was prepared by dissolving 5 g of homopolymer 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as prepared in Example 2 in 1000 mL of water. The mixture was allowed to sit for 1 hour. 450 g of melamine formaldehyde resin was subsequently added to the aqueous solution of homopolymer 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and allowed to mix with magnetic stirring for one hour. Laminate substrate paper was immersed in the melamine formaldehyde mixture and completely saturated with the solution. The saturated laminate paper was dried in an oven at 90° C. (194° F.). The laminate paper was tested using the bromophenol blue test described in Example 7. It was determined that the antimicrobial agent was homogeneously distributed throughout the saturated laminate paper.
- An antimicrobial paint formulation was prepared by adding a 0.5% concentration of homopolymer 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride prepared as in Example 2 to a solvent-borne two-component epoxy/polyamide commercial paint coating.
- Aluminum slides were spray painted with the antimicrobial paint and allowed to air dry. The painted aluminum slide was tested according to the method described in Example 5 and found to exhibit a log kill of 5.52 against E. coli.
- Example 2 One g of a homopolymer 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as made in Example 2 and 1 g of boric acid were added to one liter of distilled water with stirring. The mixture was allowed to age at room temperature for one hour. Ten 2 inch (5.1 cm) by 2 inch (5.1 cm) squares of natural unbleached cotton were immersed in the solution. The cotton swatches were removed and allowed to air dry for eight hours. One swatch was tested for antimicrobial activity according to the method described in example 5 and found to exhibit a log kill greater than 5.5 when subjected to E. coli.
- Example 2 0.5 g of a homopolymer 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as prepared in Example 2 and 0.5 g of hydantoin were added to one liter of distilled water with stirring. The mixture was allowed to age at room temperature for one hour. Ten 2 inch (5.1 cm) by 2 inch (5.1 cm) squares of natural unbleached cotton were immersed in the solution. The cotton swatches were removed and allowed to air dry for eight hours. One swatch was tested for antimicrobial activity according to the method described in example 5 and found to exhibit a log kill greater than 6.9 when subjected to E. coli.
- An antimicrobial liquid soap is prepared by adding 2.0 g of a homopolymer of 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as prepared in Example 2 to 100 mL of a commercial liquid soap formulation. Surfaces washed with the above soap including counter tops and human hands are expected to have non-detectable microbial contamination.
- An antimicrobial disinfectant is made by dissolving 2.0 g of homopolymer 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride as made in Example 2 in one liter of isopropanol. A countertop surface contaminated with E. coli is expected to be void of E. coli after it is sprayed with the above solution.
- Unbleached cotton fabric is treated with various concentration levels of both monomeric 3-(trimethoxysilyl) propyltrimethyl ammonium chloride and the homopolymer of 3-(trimethoxysilyl) propyltrimethyl ammonium chloride as prepared in Example 19.
- 2 inch (5.1 cm) by 2 inch (5.1 cm) swatches of fabric are treated by immersing them in an aqueous solution containing the respective concentration of monomeric or polymeric 3-(trimethoxysilyl) propyltrimethyl ammonium chloride for a minimum of ten minutes. The swatches are subsequently removed from the aqueous solution and air-dried overnight.
- the swatches are analyzed for antimicrobial activity using ASTM E2149-01 as described in Example 5, followed by an accelerated laundering test according to AATCC 61-1996, which simulates multiple laundering effects.
- the swatches are again analyzed for antimicrobial activity according to ASTM E2149-01 to determine the effect of laundering on the antimicrobial activity.
- Unbleached cotton fabric is treated with various concentration levels of both monomeric 3-(trimethoxysilyl) propyldimethyltetradecyl ammonium chloride and the homopolymer of 3-(trimethoxysilyl) propyldimethyltetradecyl ammonium chloride that is prepared in a similar manner to the preparation of polymeric 3-(trimethoxysilyl) propyltrimethyl ammonium chloride as in Example 19.
- the swatches are again analyzed for antimicrobial activity according to ASTM E2149-01 to determine the effect of laundering on the antimicrobial activity. It is expected that the results before and after laundering will show that those materials containing in an appropriate minimum level of monomeric 3-(trimethoxysilyl) propyldimethyltetradecyl ammonium chloride and homopolymer of 3-(trimethoxysilyl) propyldimethyltetradecyl ammonium chloride, the homopolymeric 3-(trimethoxysilyl) propyldimethyltetradecyl ammonium chloride treated cotton will exhibit superior performance when compared to the monomeric 3-(trimethoxysilyl) propyldimethyltetradecyl ammonium chloride.
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Abstract
R3N+R0 nSiX′4-nY− (II)
wherein each R and each R0 is independently a non-hydrolysable organic group; each X′ is —OR′, —OH or —O—Si, wherein R′ is an alkyl group of 1 to about 22 carbon atoms, or an aryl group of 6 carbon atoms; n is an integer of 0 to 3; and Y is an anionic moiety suitable to form the salt of the repeating units of Formula II. Also disclosed are methods of making such a polymer and imparting sustained antimicrobial properties to a substrate using the polymer.
Description
R3N+R0 nSiX4-nY− (I)
Wherein each R and each R0 is independently, a non-hydrolysable organic group; each X is, independently, a hydrolysable group; n is an integer of 0 to 3; and Y is a suitable anionic moiety to form the salt of the compound of Formula I. Such silicon containing quaternary ammonium antimicrobial agents are typically manufactured and supplied in solvents such as methanol.
R3N+R0 nSiX′4-nY− (II)
wherein each R and each R0 is independently a non-hydrolysable organic group; each X′ is —OR′, —OH or —O—Si, wherein R′ is an alkyl group of 1 to about 22 carbon atoms, or an aryl group of 6 carbon atoms; n is an integer of 0 to 3; and Y is an anionic moiety suitable to form the salt of the repeating units of Formula II.
R3N+R0 nSiX′4-nY− (II)
wherein each R and each R0 is independently a non-hydrolysable organic group; each X′ is —OR′, —OH or —O—Si, wherein R′ is an alkyl group of 1 to about 22 carbon atoms, or an aryl group of 6 carbon atoms; n is an integer of 0 to 3; and Y is an anionic moiety suitable to form the salt of the repeating units of Formula II.
R3N+R0 nSiX4-nY− (I)
wherein each R and each R0 is independently, a non-hydrolysable organic group; each X is, independently, a hydrolysable group; n is an integer of 0 to 3; and Y is a suitable anionic moiety to form the salt of the compound Formula I. Preferably, Y is a halide. The presently most preferred silicon-containing quaternary ammonium salt is where two of the Rs are methyl and one R is octadecyl, R0 is propyl, each X is a methoxy, n is 1 and Y is chloride, such that the monomeric quaternary ammonium salt is 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride.
(R1)3SiR2N+(R3)(R4)(R5)Y− (III);
(R1)3SiR2N(R3)(R4) (IV);
wherein each R1 is, independently, halogen or R6O, where R6 is H, alkyl of 1 to about 22 carbon atoms, acetyl, acetoxy, acyl, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; a block polymer or copolymer of ethylene and propylene glycol, an alkyl monoether of 1 to about 22 carbon atoms of propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; a block polymer or copolymer of ethylene and propylene glycol or the monoester of a carbonic acid of 1 to about 22 carbon atoms and propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; a block polymer or copolymer of ethylene and propylene glycol; octyphenol; nonylphenol; or sorbitan ether;
—R3—(R7)k—R4— (V)
R3N+R0 nSiX′4-nY− (II)
-
- wherein each R and each R0 is independently a non-hydrolysable organic group, such as, without limitation, an alkyl group of 1 to about 22 carbon atoms or an aryl group, for example, phenyl; n is an integer of 0 to 3; each X′ is —OR′, wherein R′ is an alkyl group of 1 to about 22 carbon atoms, or an aryl group of 6 carbon atoms. More preferably, each of the R groups is independently methyl, ethyl, propyl, butyl, octyl, dodecyl, tetradecyl or octadecyl; each of the R0 groups is independently methyl, ethyl, propyl, butyl, octyl, dodecyl, tetradecyl or octadecyl; and each X′ is —OR′, wherein R′ is methyl, ethyl, propyl or butyl; and even more preferably, methyl or ethyl. Preferably, Y is a suitable anionic moiety to form the salt of the polymer of Formula II, such as halide, hydroxyl, acetate, SO4 −2, CO3 −2 and a PO4 −2 counter ion. More preferably, Y is a halide.
-
- (a) providing a monomeric silicon-containing quaternary ammonium salt capable of forming the polymer having the repeating units of Formula II;
- (b) hydrolysing the monomer of Formula I with water to form Si(OH) groups; and
- (c) condensing the Si(OH) groups to form the polymer of Formula II, where X′ is —O—Si.
R3N+R0 nSiX′4-nY− (II)
wherein X′ is OH; and wherein the monomer and host polymer comprise functional groups capable of reacting with SiOH groups to form the copolymer. Suitable functional groups of the monomer and host polymer may include, without limitation, —OH, —C(O)OH, —NH2, —NH, —NCO or —C(O)OR11, wherein R11 may be an aliphatic, a cycloaliphatic or an aryl group. Examples of such groups, without limitation, include an aliphatic group, such as an alkyl group of 1 to about 22 carbon atoms, for instance methyl, ethyl, propyl, butyl, octyl or dodecyl; a cycloaliphatic group, such as cyclopentane or cyclohexane; or an aryl group, such as phenyl.
- A. Dry blending the antimicrobial polymer with a bulk resin (such as in powder, flake, pellets, bead form) prior to molding.
- B. Dissolving the antimicrobial polymer and bulk resin in a common solvent, then removing the solvent prior to molding.
- C. Using methods A or B to make a concentrate with a portion of the bulk resin prior to blending with the remainder of the bulk resin.
- D. Adding the antimicrobial polymer into coating and paint formulations.
- E. Dissolving the antimicrobial polymer in a solvent to enable treatment of various materials by dipping, spraying, brushing.
- F. The antimicrobial polymer can be copolymerized with other polymers as a method of incorporation into such other polymers or a bulk resin containing them.
Chemical Structure of Silicone Species |
Tri-functional silane T0 |
|
R = alkyl group |
One-degree condensation siloxane T1 |
|
R = alkyl group |
Two-degree condensation siloxane T2 |
|
R = alkyl group |
Three-degree condensation siloxane T3 |
|
R = alkyl group |
TABLE A |
The Normalized 29Si Area % or Mole % of the Chemical Components by 29Si NMR |
T1 | |||||
One- | T2 | T3 | |||
degree | Two-degree | Three-degree | |||
condensation | condensation | condensation | |||
Silane (T0) | species | species | species | Total | |
R1—Si— (OR)3 | ≡Si—O—Si | ═Si—(O—Si)2 | —Si—(O—Si)3 | Silane + T1 + T2 + T3 | |
Sample ID | (Mole %) | (Mole %) | (Mole %) | (Mole %) | (Mole %) |
HM 4100 | 0 | 3.9 | 35.6 | 60.5 | 100 |
Lot 608-138 | |||||
TABLE 1 | |||
Wt. % Monomer | Wt. % Polymer | Log Kill | (Wt.) % CTC |
0.1 | None | 77.6 | |
0.25 | 6.11 | 73.4 | |
0.5 | 75.4 | ||
0.05 | 5.92 | 75.4 | |
0.10 | 5.75 | 77 | |
0.25 | 6.18 | 78 | |
Control Carbon | 6.05 | 79.5 | |
0% active added | |||
TABLE 2 | ||||
% Active | Monomer Un- | Monomer- | Polymer Un- | Polymer |
in | laundered % | laundered % | Laundered | Laundered % |
Solution | Reduction | reduction | % reduction | Reduction |
0.010 | 22 | 0 | 27 | 0 |
0.025 | 38 | 0 | 99.7 | 99.28 |
0.050 | 95 | 98.86 | 99.7 | 99.28 |
0.075 | 99.59 | 99.19 | 99.99 | 99.91 |
0.100 | 99.99 | 99.91 | 99.99 | 99.91 |
0.25 | 99.99 | 99.99 | 99.99 | 99.99 |
Control | 0 | 0 | 0 | 0 |
Claims (56)
R3N+R0SiX′3Y− (II)
R3N+R0SiX3Y− (I)
(R1)3SiR2N+(R3)(R4)(R5)Y− (III)
—R3—(R7)k—R4— (IV)
R3N+R0SiX′3Y− (II)
R3N+R0SiX3Y− (I)
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DE602006018906D1 (en) * | 2005-05-20 | 2011-01-27 | Nitto Denko Corp | ADHESIVE ADHESIVE, ADHESIVE ADHESIVE AND SURFACE PROTECTION FILM |
EP1991624A2 (en) | 2006-02-23 | 2008-11-19 | E.I. Du Pont De Nemours And Company | Removable antimicrobial coating compositions and methods of use |
AU2007221203B2 (en) * | 2006-02-23 | 2013-02-21 | The Chemours Company Fc, Llc | Removable antimicrobial coating compositions and methods of use |
CA2725103C (en) * | 2008-05-29 | 2016-05-24 | Dsm Ip Assets B.V. | Antimicrobial polymers and their uses |
JP2011522077A (en) * | 2008-05-29 | 2011-07-28 | ビーエーエスエフ ソシエタス・ヨーロピア | Antimicrobial composition containing an antimicrobial agent covalently bonded to a polyurethane-silica interpenetrating network structure |
US8648127B2 (en) * | 2008-06-02 | 2014-02-11 | The Boeing Company | Self decontaminating chemical and biological agent resistant coating |
FR2932648B1 (en) | 2008-06-24 | 2010-07-30 | Saint Gobain Performance Plast | SILICONE ELASTOMER PRODUCT HAVING BIOCIDAL ACTIVITY. |
JP4966935B2 (en) * | 2008-09-09 | 2012-07-04 | 倉敷紡績株式会社 | How to antibacterialize fibers |
CA2685654A1 (en) * | 2008-11-14 | 2010-05-14 | Mjsi, Inc. | Toilet flush handle |
US9072396B1 (en) | 2009-03-31 | 2015-07-07 | Bellamat Llc | Antimicrobial screening runner and mat |
DE102009002477A1 (en) * | 2009-04-20 | 2010-10-21 | Evonik Degussa Gmbh | Quaternary amino functional, organosilicon compounds containing composition and their preparation and use |
CN102481757A (en) * | 2009-07-17 | 2012-05-30 | 卡尔斯特里姆保健公司 | Transparent conductive film comprising water soluble binders |
US20110177146A1 (en) * | 2009-07-27 | 2011-07-21 | E. I. Du Pont De Nemours And Company | Removable antimicrobial coating compositions containing cationic rheology agent and methods of use |
GB0914307D0 (en) | 2009-08-15 | 2009-09-30 | Dow Corning | Antimicrobial quarternary ammonium silane compositions |
WO2011103445A1 (en) | 2010-02-18 | 2011-08-25 | Tekni-Plex, Inc. | Aeration system with antimicrobial properties |
US20110233810A1 (en) * | 2010-03-25 | 2011-09-29 | W. M. Barr & Company | Antimicrobial plastic compositions and methods for preparing same |
AU2011248537B2 (en) | 2010-04-28 | 2014-04-17 | University Of Georgia Research Foundation, Inc. | Photochemical cross-linkable polymers, methods of marking photochemical cross-linkable polymers, methods of using photochemical cross-linkable polymers, and methods of making articles containing photochemical cross-linkable polymers |
DE102010031184A1 (en) * | 2010-07-09 | 2012-01-12 | Evonik Degussa Gmbh | Process for the preparation of a dispersion comprising silica particles and cationizing agents |
WO2012071494A1 (en) | 2010-11-23 | 2012-05-31 | Minntech Corporation | Anti-microbial composition |
US20140141230A1 (en) * | 2011-08-04 | 2014-05-22 | Jason J. Locklin | Permanent attachment of ammonium and guanidine-based antimicrobials to surfaces containing c-h functionality |
WO2013056007A2 (en) | 2011-10-14 | 2013-04-18 | University Of Georgia Research Foundation, Inc. | Photochemical cross-linkable polymers, methods of making photochemical cross-linkable plolymers, methods of using photochemical cross-linkable poloymers, and methods of making articles containing photochemical cross-linkable polymers |
EP2785177A1 (en) * | 2011-11-30 | 2014-10-08 | Coventry University | Antimicrobial animal product |
WO2013121222A1 (en) * | 2012-02-16 | 2013-08-22 | Arcis Biotechnology Limited | Coating compositions and methods |
US9918466B2 (en) | 2013-01-14 | 2018-03-20 | Empire Technology Development Llc | Antimicrobial polymers and methods for their production |
US9241881B2 (en) * | 2013-03-15 | 2016-01-26 | Stewart J. Lustgarten | Dental material and method |
US9675735B2 (en) * | 2013-03-15 | 2017-06-13 | Parasol Medical LLC | Catheters having an antimicrobial treatment |
US20160150778A1 (en) | 2013-04-22 | 2016-06-02 | Jansen Ag | Plastic having a biocidal surface and method for producing said plastic |
EP2824139A1 (en) * | 2013-07-12 | 2015-01-14 | Jansen AG | Plastic with a biocidal surface and method of making same |
CA3105565C (en) | 2013-04-26 | 2023-03-07 | Biointeractions Limited | Bioactive coatings |
USRE49528E1 (en) | 2013-04-26 | 2023-05-16 | Biointeractions Ltd. | Bioactive coatings |
CN107580451A (en) | 2015-01-13 | 2018-01-12 | 比奥塞恩公司 | The solid antimicrobial composition of solubility with enhancing |
US10827757B2 (en) | 2015-10-12 | 2020-11-10 | Lubrizol Advanced Materials, Inc. | Biocidally active polymer compositions |
US20170238542A1 (en) | 2016-02-23 | 2017-08-24 | Isoklean Llc | Stabilized antimicrobial compositions and methods of use |
CN106188419B (en) * | 2016-07-25 | 2018-08-21 | 东南大学 | The preparation method of graft polymers and antibacterial soft lens based on surface grafting |
US10967082B2 (en) | 2017-11-08 | 2021-04-06 | Parasol Medical, Llc | Method of limiting the spread of norovirus within a cruise ship |
US10864058B2 (en) | 2018-03-28 | 2020-12-15 | Parasol Medical, Llc | Antimicrobial treatment for a surgical headlamp system |
EP4153657A2 (en) | 2020-05-22 | 2023-03-29 | Sichem | Nano-ceramic, hybrid, transparent and biocidal coating for solid substrate, solid substrate comprising such a coating and method for obtaining same |
IT202000030179A1 (en) | 2020-12-11 | 2022-06-11 | Crossing Srl | SURFACE ANTIMICROBIAL TREATMENTS |
BE1029530B1 (en) | 2021-06-25 | 2023-01-30 | Sichem | Process for obtaining a coating |
BE1029958B1 (en) | 2021-11-24 | 2023-06-19 | Sichem | IMPROVED BIOCIDAL COATING |
CN118510840A (en) * | 2022-01-28 | 2024-08-16 | 纳米及先进材料研发院有限公司 | Antimicrobial compositions with enhanced efficacy and extended performance life and methods of making the same |
Citations (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3560385A (en) | 1968-11-01 | 1971-02-02 | Dow Corning | Method of lubricating siliceous materials |
US3695921A (en) | 1970-09-09 | 1972-10-03 | Nat Patent Dev Corp | Method of coating a catheter |
US3730701A (en) | 1971-05-14 | 1973-05-01 | Method for controlling the growth of algae in an aqueous medium | |
US3794736A (en) | 1971-09-29 | 1974-02-26 | Dow Corning | Method of inhibiting the growth of bacteria and fungi using organosilicon amines |
US3814739A (en) | 1971-12-27 | 1974-06-04 | Toray Industries | Method of manufacturing fibers and films from an acrylonitrile copolymer |
US3860709A (en) | 1971-09-29 | 1975-01-14 | Dow Corning | Method of inhibiting the growth of bacteria and fungi using organosilicon amines |
US3888728A (en) | 1972-10-18 | 1975-06-10 | Goldschmidt Ag Th | Process for manufacturing carrier sheets treated with hardenable aminoplast resin preliminary condensates for surface coating |
US4255480A (en) | 1978-02-22 | 1981-03-10 | Nevamar Corporation | Abrasion-resistant laminate |
US4282366A (en) | 1979-11-06 | 1981-08-04 | International Paper Company | Organosilicon quaternary ammonium antimicrobial compounds |
US4394378A (en) | 1981-07-08 | 1983-07-19 | Klein Stewart E | 3-(Trimethoxysilyl) propyldidecylmethyl ammonium salts and method of inhibiting growth of microorganisms therewith |
EP0090577A1 (en) * | 1982-03-24 | 1983-10-05 | Dow Corning Corporation | Insoluble polymeric contact preservatives |
US4408996A (en) | 1981-10-09 | 1983-10-11 | Burlington Industries, Inc. | Process for dyeing absorbent microbiocidal fabric and product so produced |
US4411928A (en) | 1981-10-09 | 1983-10-25 | Burlington Industries, Inc. | Process for applying a water and alcohol repellent microbiocidal finish to a fabric and product so produced |
US4414268A (en) | 1981-10-09 | 1983-11-08 | Burlington Industries, Inc. | Absorbent microbiocidal fabric and process for making same |
US4504541A (en) | 1984-01-25 | 1985-03-12 | Toyo Boseki Kabushiki Kaisha | Antimicrobial fabrics having improved susceptibility to discoloration and process for production thereof |
US4605564A (en) | 1984-01-23 | 1986-08-12 | Biological & Environmental Control Laboratories, Inc. | Coating process for making antimicrobial medical implant device |
US4614675A (en) | 1984-12-21 | 1986-09-30 | Toray Silicone Co., Ltd. | Antimicrobic, antistatic siloxane compositions and method for treating materials |
US4615937A (en) | 1985-09-05 | 1986-10-07 | The James River Corporation | Antimicrobially active, non-woven web used in a wet wiper |
US4620878A (en) | 1983-10-17 | 1986-11-04 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
US4631273A (en) | 1984-11-05 | 1986-12-23 | Dow Corning Corporation | Aqueous emulsions using cationic silanes |
US4675347A (en) | 1983-10-29 | 1987-06-23 | Unitika Ltd. | Antimicrobial latex composition |
US4842766A (en) | 1987-02-17 | 1989-06-27 | Dow Corning Corporation | Silane microemulsions |
US4847088A (en) | 1988-04-28 | 1989-07-11 | Dow Corning Corporation | Synergistic antimicrobial composition |
US4865870A (en) | 1988-07-07 | 1989-09-12 | Becton, Dickinson And Company | Method for rendering a substrate surface antithrombogenic |
EP0351957A2 (en) | 1988-07-19 | 1990-01-24 | Dow Corning Corporation | Method of making antimicrobially active surfaces |
US4999210A (en) | 1989-01-18 | 1991-03-12 | Becton, Dickinson And Company | Anti-infective and antithrombogenic medical articles and method for their preparation |
US5024875A (en) | 1986-09-09 | 1991-06-18 | Burlington Industries, Inc. | Antimicrobial microporous coating |
US5053048A (en) | 1988-09-22 | 1991-10-01 | Cordis Corporation | Thromboresistant coating |
US5064613A (en) | 1989-11-03 | 1991-11-12 | Dow Corning Corporation | Solid antimicrobial |
US5069899A (en) | 1989-11-02 | 1991-12-03 | Sterilization Technical Services, Inc. | Anti-thrombogenic, anti-microbial compositions containing heparin |
US5290894A (en) | 1986-12-23 | 1994-03-01 | Biopolymers Limited | Biostatic and biocidal compositions |
WO1994013748A1 (en) | 1992-12-04 | 1994-06-23 | Warner-Lambert Company | Durable antimicrobial surface treatment of plastic materials |
US5340583A (en) | 1993-05-06 | 1994-08-23 | Allergan, Inc. | Antimicrobial lenses and lens care systems |
US5358688A (en) | 1993-02-09 | 1994-10-25 | Ciba-Geigy Corporation | Antimicrobial quaternary ammonium group-containing polymers, compositions thereof, and monomers used to produce said polymers |
US5399737A (en) | 1994-04-04 | 1995-03-21 | Alcon Laboratories, Inc. | Quaternary ammonium siloxane compounds and methods for their use |
US5411585A (en) | 1991-02-15 | 1995-05-02 | S. C. Johnson & Son, Inc. | Production of stable hydrolyzable organosilane solutions |
EP0415540B1 (en) | 1989-08-07 | 1995-06-14 | Dow Corning Corporation | Antimicrobial rinse cycle additive |
US5624704A (en) | 1995-04-24 | 1997-04-29 | Baylor College Of Medicine | Antimicrobial impregnated catheters and other medical implants and method for impregnating catheters and other medical implants with an antimicrobial agent |
WO1997042200A1 (en) | 1996-05-07 | 1997-11-13 | Bioshield Technologies, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US5753733A (en) | 1994-01-27 | 1998-05-19 | Wacker-Chemie Gmbh | Redispersible, silicon-modified dispersion powder composition, process for its preparation and its use |
US5954869A (en) | 1997-05-07 | 1999-09-21 | Bioshield Technologies, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US5959014A (en) | 1996-05-07 | 1999-09-28 | Emory University | Water-stabilized organosilane compounds and methods for using the same |
US6113815A (en) | 1997-07-18 | 2000-09-05 | Bioshield Technologies, Inc. | Ether-stabilized organosilane compositions and methods for using the same |
WO2000054587A1 (en) | 1999-03-16 | 2000-09-21 | Coating Systems Laboratories, Inc. | Antimicrobial skin preparations containing organosilane quaternaries |
US6146688A (en) | 1997-12-23 | 2000-11-14 | Morgan; Harry C. | Method of creating a biostatic agent using interpenetrating network polymers |
US6329490B1 (en) * | 1999-03-31 | 2001-12-11 | Mitsubishi Materials Corporation | Polyhedral organosilicon compound and method for producing the same |
US6376696B1 (en) | 1999-06-19 | 2002-04-23 | Clariant Gmbh | Antimicrobial siloxane quat formulations and their preparation and use |
US20030096934A1 (en) * | 2000-12-07 | 2003-05-22 | Creavis Gesellschaft F. Techn. U. Innovation Mbh | Oligomeric silasesquioxanes and a process for preparing oligomeric silasesquioxanes |
US6632805B1 (en) | 1996-05-07 | 2003-10-14 | Emory University | Methods for using water-stabilized organosilanes |
US6762172B1 (en) | 1997-07-17 | 2004-07-13 | Nova Biogenetics, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US6790910B1 (en) * | 1999-09-09 | 2004-09-14 | Creavis Gesellschaft Fuer Technologie Und Innovation Mbh | Antimicrobial additives |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US388728A (en) * | 1888-08-28 | Washing-machine | ||
CA1010782A (en) * | 1973-02-20 | 1977-05-24 | Charles A. Roth | Articles exhibiting antimicrobial properties |
JP2603291B2 (en) * | 1988-04-19 | 1997-04-23 | 東芝シリコーン株式会社 | Fine powder of silicone resin containing quaternary ammonium group |
JP2819417B2 (en) * | 1989-04-17 | 1998-10-30 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing antibacterial silicone rubber granules |
JP3229116B2 (en) * | 1994-03-10 | 2001-11-12 | 日本バイリーン株式会社 | Cartridge filter and manufacturing method thereof |
JP2001294810A (en) * | 2000-04-12 | 2001-10-23 | Shin Etsu Chem Co Ltd | Underwater antifouling paint composition |
DE60215168T2 (en) * | 2001-05-29 | 2007-08-23 | Essilor International Compagnie Générale d'Optique | METHOD FOR TRANSFERRING A HYDROPHOBIC COATING LAYER FROM A MOLDING TO AN OPTICAL SUBSTRATE |
US20060068118A1 (en) * | 2003-08-13 | 2006-03-30 | Reeve John A | Silicon-containing treatments for solid substrates |
JP2005255858A (en) * | 2004-03-11 | 2005-09-22 | Nara Institute Of Science & Technology | Antifouling resin and method for producing the same, and antifouling coating material |
JP2005343734A (en) * | 2004-06-02 | 2005-12-15 | Hitachi Chem Co Ltd | Anti-fogging glass |
-
2006
- 2006-03-22 JP JP2008503106A patent/JP2008534714A/en active Pending
- 2006-03-22 EP EP20060739201 patent/EP1863865B1/en active Active
- 2006-03-22 CA CA 2601594 patent/CA2601594A1/en not_active Abandoned
- 2006-03-22 US US11/386,348 patent/US7858141B2/en active Active
- 2006-03-22 MX MX2007011771A patent/MX2007011771A/en active IP Right Grant
- 2006-03-22 WO PCT/US2006/010317 patent/WO2006102366A1/en active Application Filing
- 2006-03-22 US US11/386,485 patent/US7851653B2/en active Active
- 2006-03-22 WO PCT/US2006/010318 patent/WO2006102367A1/en active Application Filing
Patent Citations (61)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3560385A (en) | 1968-11-01 | 1971-02-02 | Dow Corning | Method of lubricating siliceous materials |
US3695921A (en) | 1970-09-09 | 1972-10-03 | Nat Patent Dev Corp | Method of coating a catheter |
US3730701A (en) | 1971-05-14 | 1973-05-01 | Method for controlling the growth of algae in an aqueous medium | |
US3794736A (en) | 1971-09-29 | 1974-02-26 | Dow Corning | Method of inhibiting the growth of bacteria and fungi using organosilicon amines |
US3860709A (en) | 1971-09-29 | 1975-01-14 | Dow Corning | Method of inhibiting the growth of bacteria and fungi using organosilicon amines |
US3814739A (en) | 1971-12-27 | 1974-06-04 | Toray Industries | Method of manufacturing fibers and films from an acrylonitrile copolymer |
US3888728A (en) | 1972-10-18 | 1975-06-10 | Goldschmidt Ag Th | Process for manufacturing carrier sheets treated with hardenable aminoplast resin preliminary condensates for surface coating |
US4255480A (en) | 1978-02-22 | 1981-03-10 | Nevamar Corporation | Abrasion-resistant laminate |
US4282366A (en) | 1979-11-06 | 1981-08-04 | International Paper Company | Organosilicon quaternary ammonium antimicrobial compounds |
US4394378A (en) | 1981-07-08 | 1983-07-19 | Klein Stewart E | 3-(Trimethoxysilyl) propyldidecylmethyl ammonium salts and method of inhibiting growth of microorganisms therewith |
US4408996A (en) | 1981-10-09 | 1983-10-11 | Burlington Industries, Inc. | Process for dyeing absorbent microbiocidal fabric and product so produced |
US4411928A (en) | 1981-10-09 | 1983-10-25 | Burlington Industries, Inc. | Process for applying a water and alcohol repellent microbiocidal finish to a fabric and product so produced |
US4414268A (en) | 1981-10-09 | 1983-11-08 | Burlington Industries, Inc. | Absorbent microbiocidal fabric and process for making same |
EP0090577A1 (en) * | 1982-03-24 | 1983-10-05 | Dow Corning Corporation | Insoluble polymeric contact preservatives |
US4620878A (en) | 1983-10-17 | 1986-11-04 | Dow Corning Corporation | Method of preparing polyorganosiloxane emulsions having small particle size |
US4675347A (en) | 1983-10-29 | 1987-06-23 | Unitika Ltd. | Antimicrobial latex composition |
US4605564A (en) | 1984-01-23 | 1986-08-12 | Biological & Environmental Control Laboratories, Inc. | Coating process for making antimicrobial medical implant device |
US4504541A (en) | 1984-01-25 | 1985-03-12 | Toyo Boseki Kabushiki Kaisha | Antimicrobial fabrics having improved susceptibility to discoloration and process for production thereof |
US4631273A (en) | 1984-11-05 | 1986-12-23 | Dow Corning Corporation | Aqueous emulsions using cationic silanes |
US4614675A (en) | 1984-12-21 | 1986-09-30 | Toray Silicone Co., Ltd. | Antimicrobic, antistatic siloxane compositions and method for treating materials |
US4615937A (en) | 1985-09-05 | 1986-10-07 | The James River Corporation | Antimicrobially active, non-woven web used in a wet wiper |
US4692374A (en) | 1985-09-05 | 1987-09-08 | James River Corporation | Antimicrobially active, non-woven web used in a wet wiper |
US4615937B1 (en) | 1985-09-05 | 1990-06-05 | James River Corp | |
US4692374B1 (en) | 1985-09-05 | 1990-06-19 | James River Corp | |
US5024875A (en) | 1986-09-09 | 1991-06-18 | Burlington Industries, Inc. | Antimicrobial microporous coating |
US5290894A (en) | 1986-12-23 | 1994-03-01 | Biopolymers Limited | Biostatic and biocidal compositions |
US4842766A (en) | 1987-02-17 | 1989-06-27 | Dow Corning Corporation | Silane microemulsions |
US4847088A (en) | 1988-04-28 | 1989-07-11 | Dow Corning Corporation | Synergistic antimicrobial composition |
US4865870A (en) | 1988-07-07 | 1989-09-12 | Becton, Dickinson And Company | Method for rendering a substrate surface antithrombogenic |
EP0351957A2 (en) | 1988-07-19 | 1990-01-24 | Dow Corning Corporation | Method of making antimicrobially active surfaces |
US5053048A (en) | 1988-09-22 | 1991-10-01 | Cordis Corporation | Thromboresistant coating |
US4999210A (en) | 1989-01-18 | 1991-03-12 | Becton, Dickinson And Company | Anti-infective and antithrombogenic medical articles and method for their preparation |
EP0415540B1 (en) | 1989-08-07 | 1995-06-14 | Dow Corning Corporation | Antimicrobial rinse cycle additive |
US5069899A (en) | 1989-11-02 | 1991-12-03 | Sterilization Technical Services, Inc. | Anti-thrombogenic, anti-microbial compositions containing heparin |
US5064613A (en) | 1989-11-03 | 1991-11-12 | Dow Corning Corporation | Solid antimicrobial |
US5359104A (en) | 1989-11-03 | 1994-10-25 | Dow Corning Corporation | Solid antimicrobial |
US5411585A (en) | 1991-02-15 | 1995-05-02 | S. C. Johnson & Son, Inc. | Production of stable hydrolyzable organosilane solutions |
WO1994013748A1 (en) | 1992-12-04 | 1994-06-23 | Warner-Lambert Company | Durable antimicrobial surface treatment of plastic materials |
US5358688A (en) | 1993-02-09 | 1994-10-25 | Ciba-Geigy Corporation | Antimicrobial quaternary ammonium group-containing polymers, compositions thereof, and monomers used to produce said polymers |
US5536861A (en) | 1993-02-09 | 1996-07-16 | Ciba-Geigy Corporation | Monomers for producing antimicrobial quaternary group-containing polyers |
US5340583A (en) | 1993-05-06 | 1994-08-23 | Allergan, Inc. | Antimicrobial lenses and lens care systems |
US5753733A (en) | 1994-01-27 | 1998-05-19 | Wacker-Chemie Gmbh | Redispersible, silicon-modified dispersion powder composition, process for its preparation and its use |
US5399737A (en) | 1994-04-04 | 1995-03-21 | Alcon Laboratories, Inc. | Quaternary ammonium siloxane compounds and methods for their use |
US5624704A (en) | 1995-04-24 | 1997-04-29 | Baylor College Of Medicine | Antimicrobial impregnated catheters and other medical implants and method for impregnating catheters and other medical implants with an antimicrobial agent |
WO1997042200A1 (en) | 1996-05-07 | 1997-11-13 | Bioshield Technologies, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US6221944B1 (en) | 1996-05-07 | 2001-04-24 | Emory University | Water-stabilized organosilane compounds and methods for using the same |
US5959014A (en) | 1996-05-07 | 1999-09-28 | Emory University | Water-stabilized organosilane compounds and methods for using the same |
US6632805B1 (en) | 1996-05-07 | 2003-10-14 | Emory University | Methods for using water-stabilized organosilanes |
US5954869A (en) | 1997-05-07 | 1999-09-21 | Bioshield Technologies, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US6120587A (en) | 1997-05-07 | 2000-09-19 | Bioshield Technologies, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US6469120B1 (en) | 1997-05-07 | 2002-10-22 | Bioshield Technologies, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US6762172B1 (en) | 1997-07-17 | 2004-07-13 | Nova Biogenetics, Inc. | Water-stabilized organosilane compounds and methods for using the same |
US6113815A (en) | 1997-07-18 | 2000-09-05 | Bioshield Technologies, Inc. | Ether-stabilized organosilane compositions and methods for using the same |
US6146688A (en) | 1997-12-23 | 2000-11-14 | Morgan; Harry C. | Method of creating a biostatic agent using interpenetrating network polymers |
US6572926B1 (en) | 1997-12-23 | 2003-06-03 | Biosafe, Inc. | Biostatic product using interpenetrating network polymers |
WO2000054587A1 (en) | 1999-03-16 | 2000-09-21 | Coating Systems Laboratories, Inc. | Antimicrobial skin preparations containing organosilane quaternaries |
US6613755B2 (en) * | 1999-03-16 | 2003-09-02 | Coating Systems Laboratories, Inc. | Antimicrobial skin preparations containing organosilane quaternaries |
US6329490B1 (en) * | 1999-03-31 | 2001-12-11 | Mitsubishi Materials Corporation | Polyhedral organosilicon compound and method for producing the same |
US6376696B1 (en) | 1999-06-19 | 2002-04-23 | Clariant Gmbh | Antimicrobial siloxane quat formulations and their preparation and use |
US6790910B1 (en) * | 1999-09-09 | 2004-09-14 | Creavis Gesellschaft Fuer Technologie Und Innovation Mbh | Antimicrobial additives |
US20030096934A1 (en) * | 2000-12-07 | 2003-05-22 | Creavis Gesellschaft F. Techn. U. Innovation Mbh | Oligomeric silasesquioxanes and a process for preparing oligomeric silasesquioxanes |
Non-Patent Citations (5)
Title |
---|
"The Handling and Use of AEGIS Microbe Shield(TM) Technology," Form 7E4, AEGIS Environments, Midland, MI USA Rev. Oct. 2004, pp. 1-12. |
"The Handling and Use of AEGIS Microbe Shield™ Technology," Form 7E4, AEGIS Environments, Midland, MI USA Rev. Oct. 2004, pp. 1-12. |
Merker et al., "The Reaction of Alkyl Halides with Carboxylic Acids and Phenols in the Presence of Tertiary Amines", The Journal of Organic Chemistry, vol. 26, pp. 581 and 582 (1961). |
Office Action dated May 12, 2009 in corresponding U.S. Appl. No. 11/386,348, 11 pages. |
Sauvet et al. "Biocidal Polymers Active by Contact. V. Synthesis of Polysiloxanes with Biocidal Activity" J. Appl. Polym. Sci. vol. 75, 2000, pp. 1005-1012. * |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8563020B2 (en) | 2011-05-24 | 2013-10-22 | Agienic, Inc. | Compositions and methods for antimicrobial metal nanoparticles |
US9155310B2 (en) | 2011-05-24 | 2015-10-13 | Agienic, Inc. | Antimicrobial compositions for use in products for petroleum extraction, personal care, wound care and other applications |
US9226508B2 (en) | 2011-05-24 | 2016-01-05 | Agienic, Inc. | Compositions and methods for antimicrobial metal nanoparticles |
US20150353824A1 (en) * | 2013-01-11 | 2015-12-10 | Sechem, Inc. | Color inhibitor for quaternary ammonium hydroxide in non-aqueous solvent |
US9944853B2 (en) * | 2013-01-11 | 2018-04-17 | Sachem, Inc. | Color inhibitor for quaternary ammonium hydroxide in non-aqueous solvent |
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US11178867B2 (en) | 2016-02-25 | 2021-11-23 | Nobio Ltd. | Micro and nanoparticulate compositions comprising anti-microbially active groups |
US11134676B2 (en) | 2017-08-30 | 2021-10-05 | Nobio Ltd. | Anti-microbial particles and methods of use thereof |
WO2019103316A1 (en) | 2017-11-27 | 2019-05-31 | 주식회사 엘지화학 | Superabsorbent resin composition |
US10814308B2 (en) | 2017-11-27 | 2020-10-27 | Lg Chem, Ltd. | Superabsorbent polymer composition |
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JP2008534714A (en) | 2008-08-28 |
WO2006102367A8 (en) | 2008-03-06 |
EP1863865A1 (en) | 2007-12-12 |
CA2601594A1 (en) | 2006-09-28 |
WO2006102367A1 (en) | 2006-09-28 |
WO2006102366A1 (en) | 2006-09-28 |
EP1863865B1 (en) | 2012-05-16 |
US20060223962A1 (en) | 2006-10-05 |
US7858141B2 (en) | 2010-12-28 |
MX2007011771A (en) | 2008-03-14 |
US20060217515A1 (en) | 2006-09-28 |
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